US3803105A - Polymerization catalysts - Google Patents
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- US3803105A US3803105A US00226201A US22620172A US3803105A US 3803105 A US3803105 A US 3803105A US 00226201 A US00226201 A US 00226201A US 22620172 A US22620172 A US 22620172A US 3803105 A US3803105 A US 3803105A
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- polymerization
- magnesium halide
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- hydrated magnesium
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- 239000002685 polymerization catalyst Substances 0.000 title abstract description 5
- -1 MAGNESIUM HALIDE Chemical class 0.000 abstract description 27
- 239000011777 magnesium Substances 0.000 abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 abstract description 23
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 15
- 239000005977 Ethylene Substances 0.000 abstract description 15
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 10
- 150000003682 vanadium compounds Chemical class 0.000 abstract description 10
- 150000004678 hydrides Chemical class 0.000 abstract description 8
- 230000000737 periodic effect Effects 0.000 abstract description 6
- 239000004711 α-olefin Substances 0.000 abstract description 5
- 150000001993 dienes Chemical class 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- 150000002367 halogens Chemical group 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 22
- 229910052719 titanium Inorganic materials 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 229910001502 inorganic halide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- the catalysts which are particularly useful for the polymerization of ethylene and mixtures thereof with higher alphaolefins and/ or diolefins, are prepared by activating with a hydride or an organometallic compound of a metal belonging to Groups I to I11 inclusive of the Mendelyeev Periodic Table, the product obtained by reacting a hydrated magnesium halide having the formula wherein X is halogen and n is a number greater than zero, with a halogenated titanium or vanadium compound under conditions such that the hydrated magnesium halide is converted, at least on the surface thereof, to anhydrous magnesium halide.
- British Pat. No. 904,510 describes polymerization catalysts of the so-called Ziegler type and using, as one catalyst-forming component, an inorganic halide of the anhydrous MgCl type covered by a very thin layer of a transition metal compound used in a quantity not greater than 1.0% by weight with respect to the inorganic halide. According to the British patent, also, it is necessary to use the carrier in completely anhydrous condition, in order to obtain a satisfactory catalyst.
- catalysts for the polymerization of olefins can be obtained by reacting a hydrated magnesium halide of the formula in which X represents halogen and n is a number greater than zero, with a halogenated titanium or vanadium compound under conditions such that the hydrated magnesium halide is transformed, at least on the surface thereof, into anhydrous magnsium halide, and then mixing the reaction product thus obtained with a hydride or organometallic compound of a metal belonging to Groups I to III, inclusive, of the Mendelyeev Periodic Table.
- the hydrated magnesium halide is selected trom the hydrated magnesium chlorides or bromides containing from 1 to 6 moles of water and, more particularly,
- halides from 1 to 4 moles of water.
- halides include: MgCl -6H O; MgCl -2H O; MgCl -IH O;
- the titanium or vanadium compounds used in preparing the present catalysts include the normally liquid halogenated titanium or vanadium compounds, and also the normally solid halogenated titanium and vanadium compounds which are soluble in inert solvents which do not dissolve the magnesium halides.
- Representative examples of the useful titanium and vanadium compounds are: the ttrahalides, such as TiCl TiBr VCl VBr, and Til,,; the halo-alcoholates such as, for instance,
- the preparation of the catalytic component comprising the titanium or vanadium compound is carried out by reacting the hydrated magnesium halide in an excess of a liquid halogenated Ti or V compound preheated to the boiling temperature and in general to a temperature greater than C., and then removing the excess of the Ti or V compound.
- Another method consists of dissolving the Ti or V compound in an inert solvent which does not dissolve the hydrated magnesium halides and/or the anhydrous halides formed during the reaction with the transition metal compound, and then reacting the hydrated magnesium halide with the solution so obtained, preheated at a temperature greater than 70-80 C., and preferably abovel00 C.
- the amount of the titanium or vanadium compound which remains on the support obtained by reacting the halogenated Ti or V compound and the hydrated magnesium halide can vary from very low values such as for instance 0.01% by weight to higher values such as 20% or higher, depending on the reaction conditions and on the percentage of water present in the hydrated magnesium halide.
- the conditions are such that the amount of Ti or V compound present on the support is comprised between 0.1 to 10% by weight expressed as Ti or V tetrahalide.
- the catalysts of this invention consist of the product of the reaction between:
- X is a halogen
- n is a number higher than 0, under conditions in which the hydrated halide is transformed, at least on the surface, to anhydrous magnesium halide
- the organometallic compound or hydride (b) is selected from the following group of compounds: 2 5)a, 2 5)2 4 9)3 4 9)2 L 2 s)s 3 z 5)2 4' 9)2 2 5)2 4 9)4: 4 9) E( 2 5)2-
- the molar ratio between the Al compound and the Ti or V compound is not critical.
- the molar ratio Al/Ti is preferably comprised between 50 and 1000.
- the catalysts according to the present invention are particularly useful in polymerizing ethylene or mixtures thereof with higher alpha-olefins such as propylene, butens-1, etc., and/or diolefins, particularly with regard to the yield of polymer obtained. They can also be used for polymerizing higher alpha-olefins such as propylene, butene-l, 'etc. to homopolymers.
- the polymerization is carried out in liquid phase in the presence or absence of inert solvents, or in the gaseous phase.
- the polymerization temperature may be comprised between -80 and 200 0, preferably between 50 and 100 C., at atmospheric or increased pressure.
- the molecular weight of the polymer may be regulated according to the known methods, such as, for example, by carrying out the polymerization in the presence of an alkyl halide, organometallic compounds of Cd or Zn, or hydrogen.
- the catalytic activity of the catalysts of this invention is little influenced by the presence of the molecular weight regulators.
- the polyethylene obtained is a substantially linear and highly crystalline polymer, having density values equal to or higher than 0.96 g./cm. and having characteristics of workability, especially as far as injection molding is concerned, which are very good and generally better than those of polyethylene obtained with the conventional socalled Ziegler catalysts.
- the Ti content of polyethylene prepared with the catalysts according tothe present invention is generally lower than 20 ppm. by weight.
- EXAMPLE 1 Into a glass autoclave provided with a stirrer and fitted with a filtering plate placed on its bottom there were introduced 300 cm. of TiCl Thereupon the temperature was brought to 135 C. 70 g. of MgCl -6H O free from magnesium oxychloride were then added. After one hour of reaction, the excess of TiCl was removed by hot filtration. The solid product left behind in the autoclave was repeatedly washed with boiling TiCl and then with cyclohexane at 80 C. until the disappearance of TiCL; in the washing liquid. The product was then discharged from the autoclave and dried at 100 under vacuum.
- Example 1 0.059 g. of the solid product was used to polymerize ethylene under the conditions of Example 1.
- T here were thus obtained 334 g. of polymer having an intrinsic viscosity of 2.7 dl./g.
- the yield in polymer was 209,000 g./g. Ti.
- EXAMPLE 3 75 g. of MgCl -6H O were dried for 8 hours at C. in a nitrogen stream in such a Way as to remove all the absorbed water and part of the water of crystallization.
- EXAMPLE 4 The catalytic component prepared according to Example 1 was used in the polymerization of propylene carried out under the following conditions: 1800 cc. of technical n-heptane, 4.7 g. of Al(C H Cl and 0.087 of the catalytic component comprising the carrier and prepared according to Example 1 were introduced into an autoclave having a holding capacity of 5 liters and purified with dry nitrogen. Immediately thereafter, 2.5 atm. of propylene and 0.3 atm. of hydrogen were introduced. The temperature was maintained at 70 C. The total pressure was kept constant during the polymerization by continuously feeding propylene.
- EXAMPLE 5 7 g. MgCI -GH O were reacted with 350 cc. of TiCl; under the same conditions as in Example 1. The analysis of the Washed and dried product showed the presence of 4.55% of Ti and 64.95% of C1. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl- 0.034 g. of said product was used to polymerize ethylene under the conditions of Example 1. After 6 hours there were obtained 384 g. of polymer having an intrinsic viscosity of 2.3 dL/g. The yield in polymer was 248,000 g./g. Ti.
- EXAMPLE 6 23 g. of MgCl -2H 0 were reacted with 400 cc. of TiCl under the same conditions as in Example 1. The analysis of the washed and dried product showed the presence of 3.75% of Ti and 68.5% of CI. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl 0.0425 g. of this product were used to polymerize ethylene under the conditions of Example 1. After 4 hours there were obtained 452 g. of polymer with a yield of 283,000 g./g. Ti.
- EXAMPLE 7 Into the autoclave used in Example 1 were introduced 300 cc. of TiCl The temperature was brought to 135 C. Thereupon, 7 0 g. of MgBr -6H O were introduced. After 1 hour of heating the excess TiCl was removed by hot filtering. The solid product remaining in the autoclave was repeatedly Washed with boiling TiCl, and then with boiling cyclohexane until the total disappearance of TiCh, in the washing liquid. The analysis of the solid product dried under vacuum at 100 C. showed a Ti content of 4.25% and Cl and Br contents, respectively, of 53% and 10.5%. The X-ray analysis of the product showed that it is formed prevailingly of MgCI 0.041 g.
- EXAMPLE 8 70 g. of Mgcl -H o were reacted with 300 cc. of TiCl, under the same conditions as described in Example '1. The analysis of the washed and dried product showed the presence of 0.75% of Ti and 60.2% of C1. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl No Mg(OH)Cl was found to be present.
- a process for preparing a supported catalytic component to be used with a second catalytic component consisting of a hydride or organometallic compound of a metal belonging to Group I, II or III of the Mendelyeev Periodic System for the polymerization of olefins comprising the step of reacting a hydrated magnesium bichloride containing from 1 to 6 moles of H 0 with an excess of a normally liquid titanium or vanadium halide, said excess being preheated at a temperature higher than -80 C., and thereafter removing the liquid phase from the reaction zone.
- liquid titanium or vanadium halide is selected from the group consisting of the tetrahalides of said metals.
- a process for preparing a catalyst for the polymerization of olefins consisting in reacting a supported catalytic component prepared accordinging to the process of claim 1 with a hydride or organometallic compound of a metal belonging to Group I, II or III of the Mendelyeev Periodic System.
- Col. 1 line 5 from below, magnsium should be magnesium C01. 2, line 7 from below, or after 111) should be of Col. 3, Example'l line 5 from below, v the formula A1, iC I-I 3 should appear after ,2 g. of
Abstract
NEW POLYMERIZATION CATALYSTS ARE DISCLOSED. THE CATAALYSTS, WHICH ARE PARTICULARLY USEFUL FOR THE POLYMERIZATION OF ETHYLENE AND MIXTURES THEREOF WITH HIGHER ALPHAOLEFINS AND/OR DIOLEFINS, ARE PREPARED BY ACTIVATING WITH A HYDRIDE OR AN ORGANOMETALLIC COMPOUND OF A METAL BELONGING TO GROUPS I TO III INCLUSIVE OF THE MENDELYEEV PERIODIC TABLE, THE PRODUCT OBTAINED BY REACTING A HYDRATED MAGNESIUM HALIDE HAVING THE FORMULA
MGX2''NH2O
WHEREIN X IS HALOGEN AND N IS A NUMBER GREATER THAN ZERO, WITH A HALOGENATED TITANIUM OR VANADIUM COMPOUND UNDER CONDITIONS SUCH THAT THE HYDRATED MAGNESIUM HALIDE IS CONVERTED, AT LEAST ON THE SURFACE THEREOF, TO ANHYDROUS MAGNESIUM HALIDE.
MGX2''NH2O
WHEREIN X IS HALOGEN AND N IS A NUMBER GREATER THAN ZERO, WITH A HALOGENATED TITANIUM OR VANADIUM COMPOUND UNDER CONDITIONS SUCH THAT THE HYDRATED MAGNESIUM HALIDE IS CONVERTED, AT LEAST ON THE SURFACE THEREOF, TO ANHYDROUS MAGNESIUM HALIDE.
Description
United States Patent Ofice Patented Apr. 9, 1974 Int. Cl. C08f 1/36, 3/06; B013 11/84 U.S. Cl. 260-80.78 7 Claims ABSTRACT OF THE DISCLOSURE New polymerization catalysts are disclosed. The catalysts, which are particularly useful for the polymerization of ethylene and mixtures thereof with higher alphaolefins and/ or diolefins, are prepared by activating with a hydride or an organometallic compound of a metal belonging to Groups I to I11 inclusive of the Mendelyeev Periodic Table, the product obtained by reacting a hydrated magnesium halide having the formula wherein X is halogen and n is a number greater than zero, with a halogenated titanium or vanadium compound under conditions such that the hydrated magnesium halide is converted, at least on the surface thereof, to anhydrous magnesium halide.
This is a continuation of application Ser. No. 1,859, filed Jan. 9, 1970, now abandoned.
THE PRIOR ART Dutch patent application No. 6714024 described catalysts for the polymerization of olefins consisting of the reaction product of an organometallic compound of a metal belonging to Groups I to III with the product obtained by reacting a transition metal halide with a carrier consisting of an anhydrous, oxygenated magnesium compound.
According to the Dutch patent, it is essential to use the carrier in completely anhydrous condition, in order to obtain satisfactory catalysts.
British Pat. No. 904,510 describes polymerization catalysts of the so-called Ziegler type and using, as one catalyst-forming component, an inorganic halide of the anhydrous MgCl type covered by a very thin layer of a transition metal compound used in a quantity not greater than 1.0% by weight with respect to the inorganic halide. According to the British patent, also, it is necessary to use the carrier in completely anhydrous condition, in order to obtain a satisfactory catalyst.
THE PRESENT INVENTION Surprisingly, in view of the prior art, we have found that catalysts for the polymerization of olefins, and having valuable properties, particularly a very high catalytic activity, can be obtained by reacting a hydrated magnesium halide of the formula in which X represents halogen and n is a number greater than zero, with a halogenated titanium or vanadium compound under conditions such that the hydrated magnesium halide is transformed, at least on the surface thereof, into anhydrous magnsium halide, and then mixing the reaction product thus obtained with a hydride or organometallic compound of a metal belonging to Groups I to III, inclusive, of the Mendelyeev Periodic Table.
Preferably, the hydrated magnesium halide is selected trom the hydrated magnesium chlorides or bromides containing from 1 to 6 moles of water and, more particularly,
from 1 to 4 moles of water. Examples of these halides include: MgCl -6H O; MgCl -2H O; MgCl -IH O;
MgBr -6H O and MgBr -H O.
The titanium or vanadium compounds used in preparing the present catalysts include the normally liquid halogenated titanium or vanadium compounds, and also the normally solid halogenated titanium and vanadium compounds which are soluble in inert solvents which do not dissolve the magnesium halides. Representative examples of the useful titanium and vanadium compounds are: the ttrahalides, such as TiCl TiBr VCl VBr, and Til,,; the halo-alcoholates such as, for instance,
According to the preferred method, the preparation of the catalytic component comprising the titanium or vanadium compound is carried out by reacting the hydrated magnesium halide in an excess of a liquid halogenated Ti or V compound preheated to the boiling temperature and in general to a temperature greater than C., and then removing the excess of the Ti or V compound.
Another method consists of dissolving the Ti or V compound in an inert solvent which does not dissolve the hydrated magnesium halides and/or the anhydrous halides formed during the reaction with the transition metal compound, and then reacting the hydrated magnesium halide with the solution so obtained, preheated at a temperature greater than 70-80 C., and preferably abovel00 C.
In this case it is convenient to use the Ti or V compound in an amount suflicient to react with the water contained in the hydrated magnesium halide.
The amount of the titanium or vanadium compound which remains on the support obtained by reacting the halogenated Ti or V compound and the hydrated magnesium halide can vary from very low values such as for instance 0.01% by weight to higher values such as 20% or higher, depending on the reaction conditions and on the percentage of water present in the hydrated magnesium halide.
Preferably the conditions are such that the amount of Ti or V compound present on the support is comprised between 0.1 to 10% by weight expressed as Ti or V tetrahalide.
Summing up, the catalysts of this invention consist of the product of the reaction between:
(a) the product obtained by reacting a halogenated Ti or V compound with a hydrated magnesium halide having the formula:
wherein X is a halogen, and n is a number higher than 0, under conditions in which the hydrated halide is transformed, at least on the surface, to anhydrous magnesium halide; and
(b) a hydride or organometallic compound of metals belonging to Group I, II or III or the Mendelyeev Periodic System.
Preferably the organometallic compound or hydride (b) is selected from the following group of compounds: 2 5)a, 2 5)2 4 9)3 4 9)2 L 2 s)s 3 z 5)2 4' 9)2 2 5)2 4 9)4: 4 9) E( 2 5)2- The molar ratio between the Al compound and the Ti or V compound is not critical.
For polymerizing ethylene the molar ratio Al/Ti is preferably comprised between 50 and 1000.
The catalysts according to the present invention are particularly useful in polymerizing ethylene or mixtures thereof with higher alpha-olefins such as propylene, butens-1, etc., and/or diolefins, particularly with regard to the yield of polymer obtained. They can also be used for polymerizing higher alpha-olefins such as propylene, butene-l, 'etc. to homopolymers. The polymerization is carried out in liquid phase in the presence or absence of inert solvents, or in the gaseous phase.
The polymerization temperature may be comprised between -80 and 200 0, preferably between 50 and 100 C., at atmospheric or increased pressure.
The molecular weight of the polymer may be regulated according to the known methods, such as, for example, by carrying out the polymerization in the presence of an alkyl halide, organometallic compounds of Cd or Zn, or hydrogen. The catalytic activity of the catalysts of this invention is little influenced by the presence of the molecular weight regulators.
For instance, when polymerizing ethylene, it is possible to regulate the molecular weight of the polyethylene produced in a range of practical useful intrinsic viscosi ties, determined in Tetralin at 135 C., comprised between about 1.5 and 3.0 dl./g., without a decrease in the polymer yield to a value below which it would be necessary to purify the polymer of catalyst residues.
The polyethylene obtained is a substantially linear and highly crystalline polymer, having density values equal to or higher than 0.96 g./cm. and having characteristics of workability, especially as far as injection molding is concerned, which are very good and generally better than those of polyethylene obtained with the conventional socalled Ziegler catalysts. The Ti content of polyethylene prepared with the catalysts according tothe present invention is generally lower than 20 ppm. by weight.
The following examples are given to illustrate the invention, and are not intended to be limiting.
Unless otherwise specifically indicated, the percentages reported in the examples are by weight. The intrinsic viscosity (1 of the polymers was measured in Tetralin at 135 C.
EXAMPLE 1 Into a glass autoclave provided with a stirrer and fitted with a filtering plate placed on its bottom there were introduced 300 cm. of TiCl Thereupon the temperature was brought to 135 C. 70 g. of MgCl -6H O free from magnesium oxychloride were then added. After one hour of reaction, the excess of TiCl was removed by hot filtration. The solid product left behind in the autoclave was repeatedly washed with boiling TiCl and then with cyclohexane at 80 C. until the disappearance of TiCL; in the washing liquid. The product was then discharged from the autoclave and dried at 100 under vacuum.
The analysis of the dried product gave: Ti=3.28%, Cl =52.7%.
The X-ray analysis showed that no Mg oxychloride was present and revealed the presence of anhydrous MgCl Fifty milligrams of the product thus obtained were suspended in 50 cc. of n-heptane and used to polymerize ethylene under the following conditions: into a stainless steel autoclave having a holding capacity of 1.8 liters and purified with dry nitrogen, there were introduced 1000 cc. of technical n-heptane and then 2 g. of Thereupon, the temperature was brought up to 75 C. and 0.050 g. of the catalytic component suspended in 50 cc. of n-heptane were added.
Amo nt Immediately thereafter, 3 atm. of hydrogen and 10 atm. of ethylene were introduced. The temperature rose to about C. and was maintained at 80 C.- -5 during the polymerization. The total pressure was kept constant by continuously feeding ethylene. After two hours the suspension was discharged from the autoclave. The polymer was separated by filtration, and dried at C. under vacuum.
There were thus obtained 355 g. of polyethylene having an intrinsic viscosity, in Tetralin at 135 C., of 2.5 dl./ g. The yield in polymer was 222,000 g./ g. Ti.
EXAMPLE 2 The preparation of the catalytic component described in Example 1 was repeated with the difference that the reaction took place at 100' instead of at 135 C. The analysis of the product thus obtained gave: Ti=3.04%, Cl =52.5%. The X-ray analysis showed the presence of MgCl and that no Mg(OH)Cl was formed.
0.059 g. of the solid product was used to polymerize ethylene under the conditions of Example 1.
T here were thus obtained 334 g. of polymer having an intrinsic viscosity of 2.7 dl./g. The yield in polymer was 209,000 g./g. Ti.
EXAMPLE 3 75 g. of MgCl -6H O were dried for 8 hours at C. in a nitrogen stream in such a Way as to remove all the absorbed water and part of the water of crystallization.
The X-ray examination of the product thus obtained showed the presence of significant amounts of IH O.
70 g. of the product thus obtained were reacted with TiCL, under the same conditions as in Example 1. The analysis of the washed and dried product gave a Ti content of 10.0% and a Cl content of 54.6%. On X-ray analysis Mg(OH)C1 was not found to be present.
0.015 g. of said product was used to polymerize ethylene under the same conditions as those of the preceding examples. After 4 hours there were obtained 196 g. of polymer having an intrinsic viscosity in Tetralin at C., of 2.4 dl./g. The yield in polymer was 131,000 g./ g. Ti.
EXAMPLE 4 The catalytic component prepared according to Example 1 was used in the polymerization of propylene carried out under the following conditions: 1800 cc. of technical n-heptane, 4.7 g. of Al(C H Cl and 0.087 of the catalytic component comprising the carrier and prepared according to Example 1 were introduced into an autoclave having a holding capacity of 5 liters and purified with dry nitrogen. Immediately thereafter, 2.5 atm. of propylene and 0.3 atm. of hydrogen were introduced. The temperature was maintained at 70 C. The total pressure was kept constant during the polymerization by continuously feeding propylene.
After 4 hours the reaction mixture was discharged from the autoclave. The polymer was separated by filtration and dried under vacuum at 100 C. 200 g. of partially crystalline polypropylene were obtained. The yield in polymer amounted to 71,000 g./ g. Ti.
EXAMPLE 5 7 g. MgCI -GH O were reacted with 350 cc. of TiCl; under the same conditions as in Example 1. The analysis of the Washed and dried product showed the presence of 4.55% of Ti and 64.95% of C1. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl- 0.034 g. of said product was used to polymerize ethylene under the conditions of Example 1. After 6 hours there were obtained 384 g. of polymer having an intrinsic viscosity of 2.3 dL/g. The yield in polymer was 248,000 g./g. Ti.
EXAMPLE 6 23 g. of MgCl -2H 0 were reacted with 400 cc. of TiCl under the same conditions as in Example 1. The analysis of the washed and dried product showed the presence of 3.75% of Ti and 68.5% of CI. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl 0.0425 g. of this product were used to polymerize ethylene under the conditions of Example 1. After 4 hours there were obtained 452 g. of polymer with a yield of 283,000 g./g. Ti.
EXAMPLE 7 Into the autoclave used in Example 1 were introduced 300 cc. of TiCl The temperature was brought to 135 C. Thereupon, 7 0 g. of MgBr -6H O were introduced. After 1 hour of heating the excess TiCl was removed by hot filtering. The solid product remaining in the autoclave was repeatedly Washed with boiling TiCl, and then with boiling cyclohexane until the total disappearance of TiCh, in the washing liquid. The analysis of the solid product dried under vacuum at 100 C. showed a Ti content of 4.25% and Cl and Br contents, respectively, of 53% and 10.5%. The X-ray analysis of the product showed that it is formed prevailingly of MgCI 0.041 g. of said product was used to polymerize ethylene under the conditions of Example 1. After 3 hours there were obtained 545 g. of polymer having an intrinsic viscosity of 2.3 dl./g. The polymer yield was 310,000 g./ g. Ti.
EXAMPLE 8 70 g. of Mgcl -H o were reacted with 300 cc. of TiCl, under the same conditions as described in Example '1. The analysis of the washed and dried product showed the presence of 0.75% of Ti and 60.2% of C1. The X-ray analysis showed that the product is substantially formed of anhydrous MgCl No Mg(OH)Cl was found to be present.
0.031 g. of said product was used to polymerize ethylene under the conditions of Example 1. After 4 hours there were obtained 159 g. of polymer. The yield was 757,000 g./g. Ti.
Results similar to those reported in the examples are obtained using other hydrated magnesium halides, other hydrides or organometallic compounds of the Groups I to III metals, and other titanium or vanadium compounds as disclosed.
It will be apparent that some changes in details may be made in practicing the invention without departing from the spirit thereof. Therefore, we intend to include, in the appended claims, all changes and modifications which will be obvious to those skilled in the art from the description and working examples given herein.
What we claim is:
1. A process for preparing a supported catalytic component to be used with a second catalytic component consisting of a hydride or organometallic compound of a metal belonging to Group I, II or III of the Mendelyeev Periodic System for the polymerization of olefins, comprising the step of reacting a hydrated magnesium bichloride containing from 1 to 6 moles of H 0 with an excess of a normally liquid titanium or vanadium halide, said excess being preheated at a temperature higher than -80 C., and thereafter removing the liquid phase from the reaction zone.
2. The process according to claim 1, characterized in that the hydrated magnesium bichloride is selected from the magnesium bichloride containing from 1 to 4 moles Of H20.
3. The process according to claim 1, characterized in that the liquid titanium or vanadium halide is selected from the group consisting of the tetrahalides of said metals.
4. A process for preparing a catalyst for the polymerization of olefins consisting in reacting a supported catalytic component prepared acording to the process of claim 1 with a hydride or organometallic compound of a metal belonging to Group I, II or III of the Mendelyeev Periodic System.
5. The process for the polymerization of ethylene and mixtures thereof with higher alpha-olefins and/or diolefins, characterized in that the polymerization is carried out in the presence of a catalyst prepared by the process of claim 4.
6. The process according to claim 5, characterized in that the polymerization is carried out at temperatures comprised between and 200 C. in the presence of an inert liquid and of a regulator of the molecular weight of the polymer and in that the polymer thus obtained does not require any purification treatment for the removal of catalyst residues therefrom.
7. The process according to claim 5, characterized in that the polymerization is carried out in the absence of an inert diluent.
References Cited UNITED STATES PATENTS 2,981,725 4/ 1961 Luft et a1 260-949 DA 3,238,146 3/1966 Hewitt et al. 260-949 DA 3,642,746 2/1972 Kashiwa et a1. 260-949 DA FOREIGN PATENTS 1,565,722 3/1969 France 260-949 DA JAMES A. SEIDLEOK, Primary Examiner E. J. SMITH, Assistant Examiner U.S. C1. X.R.
252-429 C; 260-853 R, 88.2 R, 93.7, 94.9 DA
STATES OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 803, 105 Dated April 9, 1974 Inventor(s) -Pao1o GALLI et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Col. 1, line 5 from below, magnsium should be magnesium C01. 2, line 7 from below, or after 111) should be of Col. 3, Example'l line 5 from below, v the formula A1, iC I-I 3 should appear after ,2 g. of
last line, the formula A1 (iC H should be 4 9 3 deleted.
Col. 4, line 4 of Example 4, the abbreviation g.- should appear after 0.087 i Signed and sealed this 31st day of December 1974.
( 8 EA L) Att'est:
M COY M G I BS ON JR C Z-'Z.- -.RSH.-*=.LL DANN- Attes-ting Officer Commissioner of Patents DRM PO105O (10-69) USCOMM-DC 5O376-P69 U.S, GOVERNMENT PRINTING OFFICE: 1969 O3G6-334,
Notice of Adverse Decision in Interference In Interference No. 100,1 52, involving Patent No. 3,803,105, P. Galli and G. Di Drusco, POLYMERIZATION CATALYSTS, final I judgment adverse to the patentees was rendered Mar. 1, 1984, as to claims 1-7.
[Oflzcial Gazette November 19, 1985.
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
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US4006101A (en) * | 1973-02-09 | 1977-02-01 | Nippon Oil Company Ltd. | Polymerization of olefins and catalysts therefor |
US4069169A (en) * | 1975-11-24 | 1978-01-17 | Mitsui Petrochemical Industries Ltd. | Process for preparation of catalyst component supported on high performance carrier |
US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
US4258159A (en) * | 1972-11-24 | 1981-03-24 | Solvay & Cie | Process for the polymerization of olefins |
US4262105A (en) * | 1970-10-20 | 1981-04-14 | Solvay & Cie | Process for the polymerization of olefins and catalytic products |
US4296223A (en) * | 1972-06-22 | 1981-10-20 | Solvay & Cie | Polymerization of olefins |
US4298721A (en) * | 1974-02-15 | 1981-11-03 | Montedison S.P.A. | Thermoplastic rubbers and process for preparing same |
US4363746A (en) * | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
US4503159A (en) * | 1983-08-19 | 1985-03-05 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
US4513095A (en) * | 1980-11-24 | 1985-04-23 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4520121A (en) * | 1983-10-28 | 1985-05-28 | Inkrott Kenneth E | Magnesium halide hydrates and polymerization catalysts prepared therefrom |
US4536487A (en) * | 1980-11-24 | 1985-08-20 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4540680A (en) * | 1980-11-24 | 1985-09-10 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4585749A (en) * | 1983-09-28 | 1986-04-29 | Phillips Petroleum Company | Process for the preparation of an olefin polymerization catalyst |
US5278118A (en) * | 1986-10-02 | 1994-01-11 | Ausimont, S.P.A. | Catalysts for the preparation of elastomeric olefinic copolymers |
US6248685B1 (en) * | 1996-05-31 | 2001-06-19 | Sasol Technology Pty Limited | Catalyst |
US20100292423A1 (en) * | 2007-12-12 | 2010-11-18 | Vugar Aliyev | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation |
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- 1972-02-14 US US00226201A patent/US3803105A/en not_active Expired - Lifetime
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US4262105A (en) * | 1970-10-20 | 1981-04-14 | Solvay & Cie | Process for the polymerization of olefins and catalytic products |
US4296223A (en) * | 1972-06-22 | 1981-10-20 | Solvay & Cie | Polymerization of olefins |
US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
US4258159A (en) * | 1972-11-24 | 1981-03-24 | Solvay & Cie | Process for the polymerization of olefins |
US4006101A (en) * | 1973-02-09 | 1977-02-01 | Nippon Oil Company Ltd. | Polymerization of olefins and catalysts therefor |
US4298721A (en) * | 1974-02-15 | 1981-11-03 | Montedison S.P.A. | Thermoplastic rubbers and process for preparing same |
US4069169A (en) * | 1975-11-24 | 1978-01-17 | Mitsui Petrochemical Industries Ltd. | Process for preparation of catalyst component supported on high performance carrier |
US4363746A (en) * | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
US4540680A (en) * | 1980-11-24 | 1985-09-10 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4513095A (en) * | 1980-11-24 | 1985-04-23 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4536487A (en) * | 1980-11-24 | 1985-08-20 | National Distillers And Chemical Corporation | Intermetallic compounds of polymeric transition metal oxide alkoxides and catalytic use thereof |
US4503159A (en) * | 1983-08-19 | 1985-03-05 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
US4585749A (en) * | 1983-09-28 | 1986-04-29 | Phillips Petroleum Company | Process for the preparation of an olefin polymerization catalyst |
US4520121A (en) * | 1983-10-28 | 1985-05-28 | Inkrott Kenneth E | Magnesium halide hydrates and polymerization catalysts prepared therefrom |
US5278118A (en) * | 1986-10-02 | 1994-01-11 | Ausimont, S.P.A. | Catalysts for the preparation of elastomeric olefinic copolymers |
US6248685B1 (en) * | 1996-05-31 | 2001-06-19 | Sasol Technology Pty Limited | Catalyst |
US20100292423A1 (en) * | 2007-12-12 | 2010-11-18 | Vugar Aliyev | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation |
US8481444B2 (en) * | 2007-12-12 | 2013-07-09 | Saudi Basic Industries Corporation | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation |
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